Photographic developers



Patented July 15, 1952 7 I 7 2,603,659 PHOTOGRAPHIC DEVELOPERS 1 Maynard S. Raasch, 'Wilmington, DeL, assignor c} to E. I. du Pont de Nemours and Company, Wilmington, Del., acorporationoLDelaware No Drawing. Application June 16, 1950,I f Serial No. 168,651

This invention relates to anew class 'ofaromatic amines. More particularly, this invention relates to a new class of nuclear-substituted pphenylenediamines which are particularly use- 'ful for photographic purposes and to developer compositions containing such compounds.

p-Phenylenediamine and its N -dialkyl derivatives are well-known photographic developers, both for. black and white and for color images. However, the known compounds of this type, have several defects, one being that these diamines arenot highly soluble in the developing solution. Another defect is their staining or fogging tendency'onphotographic emulsions. Still another defect is their irritating action on the skin of most persons. Moreover, in color development processes, the p phenylenediami'nes sometimes do not produce the desired color in the final image, Consequently, numerous derivatives of p phenylenediamine have been'proposed' in the technical literature in attempts to overcome these various defects; For example, the hydrogen atoms in the alkyl groups of theN-alkyl-substituted phenylene'diamines have been replaced by, s'olubilizing groups such as alkylene or arylene radicalslhavingj attached thereto carboxylic or, sulfonic acid groups, or thehydrogens in the phenylenenue cleus have been replaced by hydroxyalk'yl' groups or by alkyl groups joined to the nucleus through hetero atoms such as oxygen, nitrogen, or sulfur. While sulfonic and carboxylic acid groupsare effective solubilizing radicals on p-phenylenediamine, it is known that .the attachment of such groupstofthe phenylenering causes a'serio'us decreasefinlthe developing power of the resulting nuclear-substituted phenylenediamine and" ten-,- ders'the compound unsuitable for use in'iphoto graphic "developing solutions. Novel nuclear-substituted 'p-phenylenedia} mines are provided by this invention which pos sess high solubility in aqueous developing solu tions. low staining or fogging tendency, low irritancy to human skin, and desirablespectral characteristics, together with an unusually high level- -of photographic developing activity. p, .7 he new compounds of this invention are .pphenylenediamines having a carboxyl group joined to the benzene ring through a :chain of one to six carbon atoms in an alkylene radical, and having at least one alkyl group attached to one of the amino nitrogenatoms. Compounds of this type; which are particularly efiective as phow tographic developers have the carboxyl group-separated from the phenylene nucleus by a chain of at least two carbon atoms in the alkylene group. The;hi gh photographic developing activ''-' ity of the novel co mpounds.of this invention'is entirely unexpected in mayor U. S. Patent 2,163,166 which teachesthat attachment of carboxylic or sulfonic acid gmups'to th'e'pphenyl;

' enediaminenucleusexcessively weakens the de-' veloping activity of. the compounds.

-' 1Tb? 119W r s a id Q mp0unds of this inveh:

19 ve he following general'ror m; 5

wherein R is hydrogen or an alkyl radical, R is an alkyl radical, and R is analkylene radical having a chain of from one to six carbon atoms separating the carboxyl group from the benzene ring. Compounds of this typewhich are pre V ferred as photographic developers are those in which the total number of carbon atoms in the alkyl: groups R and RFisbetween '2 and 24, in which there is a chain of; at least two carbon atoms in the .alkylene radical separatingthe car-,- boxyl; group from the phenylene nucleus, and in which R is attached to the phenylene ringin a position ortho to the N'l-lz group. Suitable specific; radicals for R and; R? include methyl, ethyl, isopropyl, n-propyl, isobutylQn-butyl, n hexyl, n-heptyl, n-octyl, n-decyl andn-dodecyl. The alkali metal saltand especiall the sodium and potassium salts of the above acids constitute I important salts of the invention.

The compounds are prepared by various methods, the particular method in any specific case being dependent on the structure and size of the alkylenegroup in the compound being prepared Thus,=a pphenylenediamine having a carboiryl separated from the phenylene ring by.- the methylene group is conveniently prepared by re actingisatinwith hydrazine, heatingthe result mg hydra zone to term oxindole, 'nitrating the oxindole to- 5-nitrooxindole, reducing the nitro group and alkylating, e. g., ethylating, the nitr o oxindole to 5 -diethy1aniinooxindole, and heating this product under'pres'sure with barium hydroxide to form the barium salt of z-a'mino5-diethylaminophenylacetic acid. A pA-phenylenedi'amine having a carboxyl group separated from v. the phenylene nucleus by an alkylene chain of .two carbon atoms is prepared byconden'singmFnitrobenzaldehyde with. malonic a'eid'giedu'cing were;

reducing this product in alkaline solution to the sodium salt of 2-amino-5-diethylaminohydrocinnamic acid. Ap-phenylenediamine having a carboxyl group separated from the phenylene nu cleus by an alkylene chain of 4 carbon atoms is prepared by condensing m-nitrobenzaldehyde with acetaldehyde, condensing the resulting m 4 C. Barium Z-amino-5-diethylaminophenyl acetate A mixture of 18 parts of S-diethylaminooxindole, 30- parts of barium hydroxide octahydrate, and 200 parts of water is heated in a pressure reactor at 150 C; for.15 hours.- From the cooled reaction product the sparingly soluble barium salt of 2-amino-5-diethylaminopheny1- acetic acid is separated by filtration and washed first with water and then with ethanol. A yield or 1-? parts (-66% of the theoretical) is obtained. The salt is. recrystallized by dissolving it'in nitrocinnamaldehyde with malonic acid to form m-nitrocinnamalacetic acid, then :reducing "this nitrocinnamaldehydeobtained "as an intermedi-' ate is reacted with a'secdndmolecuIeoI acetalde hyde before being condensed with malonic acid The invention is illustratedin further detail by the following examples in which the proportions of ingredients are expressed in parts by weight unless otherwise noted.

EXAMPLE I V BARIUM 2-AMrNo-5-nm'rrrYLA rINorHENYLACETATE W *A rmi ndl V V Tasman-ire of 200parts or stannous chloride and 238 parts-of concentratedhydrochloric acid heated tb near-the boiling point is added 50 parts of :5-hitrooxiridole (prepared as de'scribed' by sflumpten lvliller, an Magan; J5 Am.-Chem. soc. 67, "4'99'=(-l9l5-)); in portions. The mixture is heated for; y -l ieur, on a -st'eam anana-then d-ilfitdtb about 31300; parts; l A Solution of -120 tea er NajCH 249 parts of water is added to the solution and hydrogn s'ulfide: is passed in iintilthe tin 'ion's'fare completel precipitated. Thefpr'ecjipitate-isffiltered elf; washed with water, and the" filtrate evaporated to about 500' parts, whreupon liiparts of crz rficerrtrated 'NHgOI-I is added. Need1esof- ;5"-arri-inooxindole separate; a yield of 25*par'ts being isolated." These needl'es,

after being recrystallized from alcohol ahd' 'aga-in from water, --have a melting point of- 190-195 C.

' -d e hy mmocr ndq e r ,A mixture of ZO partsQo *h-amiriooxindole, 5!) parts o'frwater. 41: Partsofethanol, and g tarts of ethyl iodide is heated to the b'oiling point in 'a reaction-vessel fitted with a reflux condenser: for 1 hourkfAfte'r coolin "the reaction f inixtire slightlythere addedfii parts or NaQ H; dissolved in ,lo parts of water andiizLfi parts-ofthyl iodide after which the mixtureis againheajted under jrefiuxfor one hour. "Ajfina'l additiorrof 5.4 parts of N 901i is n'iadegand refluxing iscontinue'd for another 2-hour. The ethanol is boiled off-and the product separates as anfoil whichcrystallizes on cooling. k'Ihe yield of 5--diethylan in o- 0Xi11d0 16flS 23 parts; corresponding to of the theory-f TheLproduct after recrystallization f om 'methanol, adding ethanol and boiling to remove them thanol.

Anal. calcd. at (C12H17O2N2)2Ba-H2OI N.

product with ferrous sulfate to m-amin'ociir-xf Found: 935%" 934% namalacetic acid, alkylating, e. g., with .ethyl i0;

The barium salt is readily soluble in alkaline carbonate developing solutions from which the insoluble barium carbonate formed as a byproduct can be removed by. filtrationand it has wdfle lepingac i I EXAMPLEII". 2-iimivoe5-iimrnrmir uoirYoIiocmNA MAra A; m-Dz'ethylaminocinndmie acid I A solution for 75 i parts of m aminocinnainic aci df (preparedf' by OQnden'si'ng m-nitrobenzalde hyde with malonic acid 'by' the method of Slotta, Ber; 68B, 187 (1935,) and" reducing the product with ferrous hydroxide by the'methodof'Gabriel;

nep ajzosa .(1883) "and 18.4; parts of-NaOH in 1 00" parts of water and eel parts" or ethanol is place 'din a reaction vessel'fitted' with a reflux condenser, '72'parts of ethyl iodide is added and the mixture is heated underfreflux for '1 hour. Asolution of 18:4 parts of NaOH in 30 parts of water'and 76' parts of ethyl iodide are added and.

the refluxing is, continued for another hour. A final 18.4 parts 'of 'NaOH in 30 parts of water is added and the heating continued for another hour at reflux temperature. The resulting solution is cooled and the m-diethylaminocinnamic 30161. is precipitatedby the careful addition of acetic acid; jRecrystalli'zation of this acid from dilute ethanol gives 75 a yield of 73%of' the theoretical, ofyellow needles'meltingja't.128-131C.V

B; :Sodium ,-1mediethylaminohydrocinnamate A mixture; of 38 parts lOf m diethylaminocinnamic acid. T parts -offlsodiumhydroxide, 100 parts r wateryjand 5- parts of nickel alloy skele ton catalystis charged into a pressure reactor capable of being agitated, 'and hydrogenated at LOGO-2,000 lb./ sq. inxhydrogenpressure at 75 C. for two hours. The produc't'is filtered, 'thefil trate evaporated to dryness and the residue used without furtherpurification;

CQ- 2,- m'ti17oso -5%diethylaminohydrocimiam ic A mixture of42 parts of sodium m-diethyb aminohydrocinnamate, 6O parts'of concentrated hydrochloric acid and IO O parts of water is cooled to Qf C. andstirred' in a reaction vessel. flo this mixture is added dropwise' 12.5' par ts' of sodium nitrite in 20 partsof water, the reaction mixture being'heId at a temperature" below '3" C. Them-ixture is allowed to' s'tar'1d for one hour, and the resulting slurry 0f yellow hydrochloride which is formed is dissolved 'bydiluting the mix ture to about 450=parts with -water.- The salt is converted to "the 'free amino acid by adding 40 parts of sodium acetate-infill parts of water. The green nitroso compound separates in crysparts, corresponding to I talline form, amounting to -ayield' of 37 parts, and melting-at 136 C. After {crystallization from methanol the 2'nitroso-.-5-diethylaminohydrocinnamic acid meltsat 137C.

'Anal.": calcd. for C13H19N20a1- i Foundz N, 11.17%, 11.21%.

" D. Sodium 2-amino-5-diethylaminohydro cinnamaie A'solution of -34 parts of 2-nitroso-5-diethylaminohydrocinnamic acid-and'5.5 parts of NaOH in 150 parts of water is charged into a pressure reactor with 5 parts of nickel alloy skeleton catalyst, and heated at 60 C. under LOUD-2,000 lb./sq. in. hydrogen pressure for 3 hours. After removing the catalyst from the reaction mixture by filtration, the filtrate is adjusted to a pH of 9.8 with sodium'carbonate and then evaporated to dryness under reduced pressure; Thi residue is dissolved in methanol, filtered, evapo rated to small volume and precipitated out in crystalline form by the slow addition of diethyl ether. A'yield of 27 parts, corresponding to 84% of the theoretical, of sodium 2-amino-5- diethylaminohydrocinnamate is obtained. This compound is readily soluble in aqueous photographic developing solutions, has very good photographic developing activity, and is no more irritating to skin than the common black and white developer p-hydroxymethylaniline, and is less irritating than p-aminodiethylaniline. This low degree of irritancy is predicated on the results of tests on guinea pigs in which the intradermal injection of sodium 2-amino-5-diethylamino-hydrocinnamate produced no more'reaction than similar injections of p-hydroxymethylaniline.

EXAMPLE III. SoDroM 2-AMINO-5-DIMETIHYLAMINQHYDBOCINNAMATE A. m-Dimethylaminocinnamic acid A mixture of 41 parts of m-ami'nocinnamic acid, parts of sodium hydroxide, 60 parts of water, 24 parts of 'methanol and 38 parts 'of methyl iodide is placedin a reaction vessel fitted with a reflux condenser and-heated to reflux-temperature for 45 minutes. There is then added a solution of 10 parts of sodium hydroxide in 25 parts of water, and, after cooling, 38 parts of methyl iodide- The mixture is again heated to reflux temperature for 45 minutes, then'another 10 parts of NaOH in 25 parts of water is" added aiter which the mixture is refluxed for another 45 minutes. The reaction mixture is neutralized with hydrochloric acid whereupon m-dimethylaminocinnamic acid precipitates as the inner salt. This salt is recrystallized from dilute ethanol. There is also formed under the above reaction conditions the quaternary ammonium iodide which is thermally decomposed to m-dimethylaminocinnamic acid by heating at 220 C. for 5 minutes. On recrystallization from dilute ethanol them-dimethylaminocinnamic acid has a melting point of 127-130 C. a 1

Anal. calcd. for CIIHIBNOZI N, 7.33%." Found: N, 7.38%, 7.21%.

B. Sodium m-dimethyZaminohiudrocinnamate A mixture of 6.6 parts of m-dimethylaminocinnamic acid, 1.4 parts of NaOH, 50 parts of water and 3 parts of nickel alloy skeleton catalyst is placed in a pressure reactor and heated at 75 C. under 1500 lb./sq. inJhydrogen-pressure for 2 hours. The resulting product is filteredto remove the catalyst and the filtrateused without further purification in the following steps;

C. 2 nitroso-5-dimethylaminohydrocinna'riiic v "V acid .To the, filtered reaction product of step 3 is added 11.9 parts of concentrated hydrochloric acid and the mixture cooled to 0 C. To this mixture is added dropwise below the surface a solution of 2.5 parts of sodium nitrite in 5 parts of water, and the resulting mixture is allowed to a d..in 1. r our. h r d t warmed to dissolve the separated solids and then asolution o f 16;-parts of sodium acetate in 40 parts-of water. is added. A-brownsolid separates' which is filtered it and washed with water. The washed solid, amounting to 5.6 parts, is dissolved in :ethanol to form a green solution Irornwhich well-formed, brown needles of 2- nitroso-5-dimethylaminohydrocinnamic acid separate, This compound has a melting point of 167 (t with decomposition.

Anal. calcd. for C11H14N2O32 N, 12.38%, 12.68%, 12.91%.

D. Sodium 2 -amino 5-dimethylaminoh cinnamate I N, 12.61 7.x, Found:

dro-

' A mixture of 2.8.parts of 2-nitroso- 5 -dimethylarninohydrocinnamic acid, 0.47 part of NaOH and 50 parts of water is charged into a pressure reactor and heated at 60 C. under 1500 lb./ sq. in. hydrogen pressure for two hours. The reaction mixture is filtered, the filtrate evaporated to dryness under reduced pressure, and the residue takenup with methanol,.treated with decolorizing carbon, filtered,-evaporated to small volume and the salt precipitated by slow addition of diethyl ether. There is obtained 2.64 partsof sodium 2-amino-5wdimethylaminohydrocinnamate.

This compound is soluble in water and forms photographic developing solutions of good activity.

EXAMPLE IV A. m-Nitrocz'nnamalacetic acid A mixture of 50 parts of m-nitrocinnamalde hydedprepared as described by Gohring, Ber.*18, 720 (1885)), 30 parts of malonic acid and 29.5 parts of pyridine is placed in a reaction vessel fitted with a reflux condenser-and heated at reflux temperature for 6 hours. On cooling to10 C. 18 parts of yellow crystals separate and they are removed by filtration. The filtrate is poured into water and sulfuric acid added to complete the precipitation, whereupon an additional quantity of solid is obtained which is purified'by dissolving in dilute alkali, treating with charcoal and precipitating with sulfuric acid. An additional 18 parts of product is obtained in this step of the process. On recrystallization ofboth of these fractions there is obtained 15 parts of mnitrocinnamalacetic acid melting at 238-243" 0., obtainedmostly from the fraction which crystallized from the original pyridine reaction mix- B. m-Aminocinnamalacetic acid A solution of 5.8 parts of concentrated ammonium hydroxide and 20 parts of m-m'trocim namalacetic acid in 30 parts of water isadded to a mixture of 165 parts of ferrous sulfate, 150 partsof water and 72 parts of concentrated ammonium hydroxide. This mixture is heated to the boiling point andleft on a steam bath for one hour. The'product is then made distinctly alkaline with ammonium hydroxide, filtered while still hot, and the filter cake Washed with hot Water, the ammonium salt being rathersparin'gly soluble. The filtrate is reduced in volume to about"500 parts andthe m-aminocinnamalacetic acid is precipitated from the solution with acetic acid. Fifteenparts of-crude product isobtained which on recrystallizationfrom ethanol amounts to 11 parts, corresponding to a yield of 64%. of the theoretical, of yellow needles of m-aminocinnamalaceticacid melting at 177-178" C.

7 Anal. calcd. for CuHuNOz: N, 7.40%. -Found: N,7.40%,7.30%. r v I C. m-Diethylaminocinnamalccetic acid To a solution of 10.7 parts of m-aminocinnamalacetic acid and 2.3 parts of NaOH in 25 parts of water and 20.5 parts oi ethanol is added 9 parts of ethyl iodide and the mixture is heated under reflux for 0.8 hour. An additional 2.3 parts of'NaOH in parts of Water and 9 parts of ethyl iodide are added and the refluxing 'is'continued for another 0.8 hourj After a final addition of 2.3 parts of NaOH and further refluxing for 0.5 hour, the solution is cooled and the m-diethylaminocinnamalacetic acid is precipitated by the addition of acetic acid. On recrystallization of the product from'dilute ethanol there is obtained 9.7 parts, corresponding to a yield of 70% of the theoretical, oi bright yellow crystals melting at 120-122 C.

Anal. calcd; for CH19NO2: N, 5.71%. Found: N, 5.54%, 5.36%. t

D. Sodium a-(m dz'ethylmnmophenyhoalerate A solution of 9.5 parts of m-diethylaminocinnamalacetic acid and 1.6 parts of NaOH in 120 parts of water is chargedinto a pressure reactor with 5 parts of nickel alloy skeleton catalyst. The mixture is heated at 75-80 C. under 2,000 1b,./ sq. in. hydrogen pressure for 2.5 hours. After the catalyst is removed by filtration thefreaction mixture is used directly in the'following step.

' E. '2- (fi-carboxybutyl) 4-dicthylamino-4 -m'- troazobenzene The solution from step Dabove is mixed with 8.3Iparts of concentrated hydrochloric acid'with added to a diazonium solution prepared: from 5.7 parts of p-nitroaniline, and 18 parts of'sodium acetate is then added and the mixture allowedtto standl hour at C. There is obtained by filtration 12 parts of 2-(6-carboxybutyl)-4-diethyl amino-4 -nitroazobenzene, corresponding to 77% of the theoretical. Recrystallization from meltingat 173-175f 0.

F. Sodium'6- (2-amino-5-diethylaminophenyl) oalerate methanol gives 10.8 parts of maroon needles 7 The reaction mixture 7 8 Theresidue is warmed with 60 parts oiacetone; cooled, filtered, and washed with acetone; tore: move p-phenylenediaminec The residueoisodium 6- (2-amino-5-diethylaminophenyl)yalerate A xt 11 t ceffhme hy bqs y i (prepared as described in organic Syntheses 24 63 (1944) 2,450 parts of z2B denatured;,ethyl alcohol, and, 8 parts of palladium-on-carbon catalyst are charged into a pressure reactor and heated at 110-120 C. for 4 .hours ,under 2, 000 1b.,fsq. in. hydrogen pressure. The reaction mixture is filtered to remove the catalyst and the filtrate is evaporated to dryness. The residue is extracted with diethyl ether, the ether extract evaporated to dryness and the. residue. recrystallized from ethyl acetate. There is obtained ,51 parts, correspondingtdal45 yield, of l-methyl:- hydrocarbostyril, having a melting point of 9'2-97 C. I I H B. 6-mtro-4-methylhydrocarbostyril A mixture of 56 parts of 4-methymydrocarbostyril and 322 parts of concentrated. sulfuric acidis placed in a reaction vessel fitted'with a thermometer, stirrer and dropping funnel 'and surrounded by an ice-salt mixture. To the reaction mixture, maintained at -3 to 0 C., is added dropwise 22.5 parts of fuming nitric acid. After standing in ice for one-half hour the mixture is poured onto 1,000 parts of ice. The solid reaction product is filtered off, washed with water and recrystallized from glacial acetic acid. A yield of 56 parts, corresponding to 78% of the theoretical, of pale yellow needles of 6-nitro-4- methylhydrocarbostyril, having a melting of 218-228 9, is-obtained.

C. (i -amino-4miethylhydvocarbostyril A mixture of 65 parts of iron povvder and 110 parts of Water is placed in a reaction vessel fitted with a stirrer and heatedto C. To this mixture are added 7.1 parts of concentrated hydrochloric acid, and- 54 parts of 6-7nitrol-metliylhydrocarbostyril in portions. After all has been added the mixture is stirred and. heated at 95 C. for 1 hour, Six parts of sodium bicarbonate and 327 parts of ethanol are then added and" the mixture is filtered hot and the residue washed with hot ethanol. Evaporation of the filtrateto dryness, and recrystallizationof the residue from dilute methyl alcohol gives 43 parts,.correspondmg to 94 of the theoretical, of G-amino-L- methylhydrocarbostyril," having a melting point of l92-203 C.

D. 6-diethylamino-4methylhydrocarbostyril .parts of ethyl iodide. After heating under repoint flux. for another 3 hours Jan additional 5.9 parts of NaOH in 10 parts of water is added and the heating continued for 1 hourunder reflux. The ethanol is distilled off the reaction mixture, whereupon the product separates as an oil which crystallizes on cooling. There is obtained 31 parts, corresponding to a yield of 94% of the theoretical, of 6-diethylamino-'-4-methylhydrocarbostyril. On recrystallization from dilute ethanol this compoundy-has a melting point of 125-128 C. E. Barium 13-(Z-amino-S-diethylaminophenyl)- i sbutyrata A mixture of 2; parts of"6' 1ethylamino-4'- methylhydrocarbostyril zzparts of barium hydroxide octahydrate, and;- 200 parts of water-is heateddnsa-closed reaction -;vesselat 150 C. for 1 h r h r a t n; mix umz filtered an 15 parts of unreacted starting; material is removed.- Barium hydroxide is then removed from the'filtrate by the addition; of solid carbon'dioxide :Thesolution is then filtered from the insoluble barium carbonate; and the filtrate is evaporated to drynesstoqgive the barium salt of }8- (2-amino-5-diethylaminophenyl) butyric acid. This product has rapid developing'action when used as a photographic developeini '1 In addition to the compounds shown in the examples, this invention includes as new products any p-phenylenediamines having a carboxyl group joined to a carbon atom of the phenylene nucleus through a chain of 1 to 6 carbon atoms in an alkylene radical, having a free NH2 group and having at least one alkyl group attached to the other amino nitrogen atom. Other specific compounds of this type, v

which are included by the general formula:

RCOOH wherein R is an alkylene radical having a chain of 1 to 6 carbon atoms separating the carboxyl group from the benzene ring, R is a hydrogen atom or an alkyl radical and R is an alkyl radical, are: zeta-(2-amino-5-diethylamino)- enanthic acid, 2-amino-5-diisobutylaminohydrocinnamic acid, 2-amino-5-di-noctylaminohydrocinnamic acid, 2-amino-5-di-n-dodecylaminophenylacetic acid, and 2-monoethylamino- S-aminohydrocinnamic acid. Compounds in which the carboxyl group readily unites with the free amino group to form acyclic amide are conveniently isolated as a salt to prevent this reaction.

The compounds of this invention are particularly useful as color developers because of the desirable combination of properties which they possess. They are highly soluble in photographic developer solutions and have low staining or fogging tendencies. They are also especially desirable since they exhibit decreased irritancy to skin in comparison with the usual N,N-dialky-pphenylenediamines. These compounds also possess a high level of developing activity, those compounds in which the carboxyl group is sepparated from the phenylene nucleus by a chain of two or more carbon atoms being especially preferred because they are the most active from this standpoint. The carboxyalkyl groups in the products of this, invention cause a bathochromic shift in the developed dyes in color-former photographic emulsions of 7-17 millimicrons greater than the shift obtained in such color films by conventional developers having a methyl group attached to the phenylene nucleus. The compounds of this invention. may be used in developing compositions containing color formers for color development of exposed silver halide contained either inthe. conventional gelatin or in a'synthetic resin carrier, and of. film-containing immobile color former incorporated in the film, particularly film having, as the silver halide binder, polyvinyl acetals of color-forming aldehydes as described in U. S. Patent 2,397,864. The nuclear-substituted p-phenylenediamines of this invention can be employed in solution with conventional developing ingredients including alkaline materials, e. g., sodium or potassium carbonate, 'b'orate, phosphate o'r hydroxide; watersoluble sulfites, e. g., ammonium sulfite, sodium sulfite and potassium sulfite. They may also be employed with such ingredients as hydroxylamine, amines, etc.

In addition to their use in photographic developing compositions which constitutes one aspect of this invention, the nuclear-substituted p-phenylenediamines of this invention, having a carboxyl group attached through an alkylene group to the phenylene nucleus, are useful as rubber accelerators, antioxidants for gasoline, stabilizers for halogen-containing plastics, azo and azomethine dye intermediates, etc., and as intermediates for preparing light-sensitive diazotype materials.

As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

l. The chemical compounds taken from the group consisting of compounds of the formula:

R-ooon wherein R is a member taken from the group consisting of hydrogen and alkyl radicals of l to 12 carbon atoms, R is an alkyl radical of l to 12 carbon atoms, and R is a saturated aliphatic hydrocarbon radical having an alkylene radical of l to 6 carbon atoms joining the benzene nucleus and 000K group, and their alkali metal salts.

2. The chemical compounds of the formula:

I NH:

wherein R is an alkyl radical of 1 to 12 carbon atoms and R." is a polymethylene radical of 2 to 6 carbon atoms.

V V ,Tle chemiel cpmbp lihd ef the formul aL omcmcmcmoo'on 12 V ffi The chemicall compound of the fotxpuig" 

1. THE CHEMICAL COMPOUNDS TAKEN FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA: 